FR2519191A1 - ACTIVE MATERIAL FOR LEAD-ACRYLIC ELECTRODES - Google Patents
ACTIVE MATERIAL FOR LEAD-ACRYLIC ELECTRODES Download PDFInfo
- Publication number
- FR2519191A1 FR2519191A1 FR8124214A FR8124214A FR2519191A1 FR 2519191 A1 FR2519191 A1 FR 2519191A1 FR 8124214 A FR8124214 A FR 8124214A FR 8124214 A FR8124214 A FR 8124214A FR 2519191 A1 FR2519191 A1 FR 2519191A1
- Authority
- FR
- France
- Prior art keywords
- lead
- electrodes
- polymer
- material according
- fact
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
MATIERE ACTIVE POUR ELECTRODES D'ACCUMULATEURS AU PLOMB. CETTE MATIERE COMPREND DU PLOMB, OU DE L'OXYDE DE PLOMB PBO, OU UN MELANGE DE PLOMB ET D'OXYDE DE PLOMB. ELLE COMPORTE EN VOLUME, DE 15 A 50 D'UNE MATIERE SYNTHETIQUE CONDUCTRICE CONSTITUEE PAR AU MOINS UN POLYMERE DOPE PAR DES IONS, LEDIT POLYMERE ETANT CHOISI DANS LE GROUPE FORME PAR LE POLYPYROL CHN, LE POLYPARAPHENYLENE CH ET LE POLYACETYLENE CH.ACTIVE MATERIAL FOR LEAD ACCUMULATOR ELECTRODES. THIS MATERIAL INCLUDES LEAD, OR LEAD OXIDE PBO, OR A MIXTURE OF LEAD AND LEAD OXIDE. IT CONTAINS IN VOLUME, FROM 15 TO 50 OF A CONDUCTIVE SYNTHETIC MATERIAL CONSTITUTED BY AT LEAST ONE POLYMER DOPED BY IONS, SUCH POLYMER BEING CHOSEN FROM THE GROUP FORMED BY POLYPYROL CHN, POLYPARAPHENYLENE CH AND POLYACETYLENE CH.
Description
Matière active pour électrodes d'accumulateurs au plombActive material for lead accumulator electrodes
L'invention concerne les matières actives pour électrodes d'accu- The invention relates to active substances for charging electrodes
mulateurs au plomb, comportant du plomb, ou de ltoxyde de plomb Pb O 2, ou lead emulators, containing lead, or lead oxide Pb O 2, or
un mélange de plomb et d'oxyde de plomb Pb Q 2. a mixture of lead and lead oxide Pb Q 2.
Au cours de la décharge de ces accumulateurs, en présence d'acide During the discharge of these accumulators, in the presence of acid
sulfurique agissant comme électrolyte, on constate au niveau des élec- sulfuric acid acting as an electrolyte, we can observe at the level of
trodes la coexistence de deux phases solides: une première phase conductrice correspondant à l'espèce chargée Pb et/ou Pb O trodes the coexistence of two solid phases: a first conductive phase corresponding to the charged species Pb and / or Pb O
une seconde phase isolante correspondant à l'espèce déchargée. a second insulating phase corresponding to the discharged species.
Les proportions relatives de ces deux phases varient au cours de la décharge. The relative proportions of these two phases vary during the discharge.
La résistance électrique du mélange espèce chargée-espèce déchar- The electrical resistance of the mixture species charged-species discharges
gée varie donc au cours de la décharge et on constate que cette variation suit une loi du type loi de percolation, ce qui se traduit par un accroissement brutal de la résistance à partir d'un certain seuil Ce Therefore, this variation follows a law of the percolation law type, which results in a sharp increase in the resistance from a certain threshold.
seuil est atteint lorsque le mélange des phases comporte en volume envi- threshold is reached when the mixture of phases
ron 65 à 70 % de matière déchargée. 65 to 70% of material discharged.
L'utilisation de l'accumulateur n'étant plus possible lorsque ce seuil est atteint, on peut donc considérer que l'électrode comportait en Since the use of the accumulator is no longer possible when this threshold is reached, it can therefore be considered that the electrode
volume, environ 30 % à 35 % de matière chargée inutile. volume, about 30% to 35% of useless charged material.
Pour améliorer les performances massiques de ces électrodes, on a alors pensé à introduire dans celles-ci du graphite Toutefois, on a constaté que dans les électrodes positives le graphite se transformait en CO 2 qui se dégageait Pour les électrodes négatives, si l'on a bien constaté une certaine amélioration pour les premières décharges, on s'est aperçu qu'ensuite apparaissaient des problèmes de contrainte entre To improve the mass performance of these electrodes, it was then thought to introduce in them graphite. However, it was found that in the positive electrodes the graphite was transformed into CO 2 which was released for the negative electrodes, if one Although there was some improvement in the first discharges, it became apparent that later there were problems of
le graphite et le plomb, qui étaient préjudiciables au bon fonctionne- graphite and lead, which were detrimental to the proper functioning
ment des accumulateurs.accumulators.
L'invention permet de remédier à ces inconvénients et d'obtenir The invention makes it possible to remedy these drawbacks and to obtain
des électrodes présentant des performances massiques améliorées, suscep- electrodes with improved mass performance, likely to
tibles de subir des nombreux cycles charge-décharge sans détérioration. tible to undergo numerous charge-discharge cycles without deterioration.
Elle a pour objet une matière active pour électrode d'accumula- It relates to an active substance for accumulator electrode
teurs au plomb, comprenant du plomb, ou de l'oxyde de plomb Pb O 2, ou un mélange de plomb et d'oxyde de plomb Pb O 2, caractérisée par le fait -2 qu'elle comporte, en volume, de 15 à 50 % d'une matière synthétique conductrice constituée par au moins un polymère dopé par des ions, ledit polymère étant choisi dans le groupe formé par le polypyrol (C 4 H 3 N), le lead-acid batteries, comprising lead, or lead oxide Pb O 2, or a mixture of lead and lead oxide Pb O 2, characterized in that it comprises, by volume, 15 at 50% of a conductive synthetic material constituted by at least one polymer doped with ions, said polymer being chosen from the group formed by polypyrol (C 4 H 3 N),
polyparaphénylène (C 6 H 4)n et le polyacétylène (CH)n. polyparaphenylene (C 6 H 4) n and polyacetylene (CH) n.
Le polymère dopé peut être représenté par les formules: l(C 4 H 3 N)Y, y A n lCH 4, y A n l(CH)y, y Al n A étant l'ion dopant The doped polymer may be represented by the formulas: ## STR1 ## wherein A is the doping ion
y, compris entre O et 1, représentant la fraction de A par monomère. y, between 0 and 1, representing the fraction of A per monomer.
Avantageusement, y est compris entre 0,02 et 0,35. Advantageously, y is between 0.02 and 0.35.
Selon une caractéristique de l'invention, les ions dopant sont donneurs d'électrons et sont choisis dans le groupe formé par C 104, According to one characteristic of the invention, the doping ions are electron donors and are chosen from the group formed by C 104,
Fe C 13, A Fs, SO 4, et H 504.Fe C 13, A Fs, SO 4, and H 504.
Selon un mode d'exécution, ladite matière synthétique est sous forme de poudre dont les grains présentent un diamètre compris entre 1 et According to one embodiment, said synthetic material is in the form of a powder whose grains have a diameter of between 1 and
microns.microns.
Selon un autre mode d'exécution ladite matière synthétique est sous forme de fibres présentant un diamètre compris entre 1 et 15 microns. En fait, l'invention revient à remplacer dans les électrodes selon l'art antérieur la partie de la matière chargée, qui ne réagissait pas, According to another embodiment, said synthetic material is in the form of fibers having a diameter of between 1 and 15 microns. In fact, the invention amounts to replacing in the electrodes according to the prior art the part of the charged material, which did not react,
par un matériau inactif vis-à-vis de l'air et de l'électrolyte, présen- by a material which is inactive with respect to air and electrolyte,
tant une densité inférieure à celle de ladite matière chargée et une a density lower than that of said charged material and a
conductivité électrique de même ordre. electrical conductivity of the same order.
Ces conditions sont réunies avec le polypyrol et le polyparaphény- These conditions are met with polypyrol and polyparaphenyl
-1 -1-1 -1
lène dont les conductivités se situent vers 80 ohm cm, ainsi que lene whose conductivities are around 80 ohm cm, as well as
par le polyacétylène.by polyacetylene.
L'invention a bien entendu également pour objet les accumulateurs The invention of course also relates to accumulators
dont les électrodes comportent de telles matières actives. whose electrodes include such active materials.
-3 - La figure annexée représente la variation du rapport R de la conductivité en décharge sur la conductivité initiale en fonction de la variation du pourcentage P de matériau isolant apparaissant dans une The appended figure shows the variation of the ratio R of the discharge conductivity on the initial conductivity as a function of the variation of the percentage P of insulating material appearing in a
électrode d'accumulateur au plomb au cours de la décharge. Lead-acid battery electrode during discharge.
Le rapport R a été porté en ordonnée et le pourcentage P en abscisse On s'aperçoit que lorsque ce pourcentage est voisin de 70 % le The ratio R has been plotted on the ordinate and the percentage P on the abscissa. It can be seen that when this percentage is close to 70% the
rapport, qui était à l'origine de 1, tend brutalement vers 0. ratio, which was at the origin of 1, tends brutally to 0.
On a réalisé des électrodes témoins comportant des pâtes classi- Control electrodes having conventional pasta were made.
ques ainsi que des électrodes conformes à l'invention et on a mesuré les as well as electrodes according to the invention and the
pourcentages d'utilisation de la matière active en décharge. percentages of use of the active ingredient in landfill.
Les électrodes témoins ont été obtenues à partir des compositions suivantes: positive H 2 SQ 4 (d: 1,40) 66 cc H 20 120 cc Pb O 1 kg négative H 2 SO (d: 1,40) 66 cc 2 4 H 20 120 ce Pb O 1 kg Ba SO 4 0,6 g vanisperce 1,5 g poudre de chène 2 g noir de fumée 1,5 g The control electrodes were obtained from the following compositions: positive H 2 SQ 4 (d: 1.40) 66 cc H 120 120 cc Pb O 1 kg negative H 2 SO (d: 1.40) 66 cc 2 4 H 20 120 this Pb O 1 kg Ba SO 4 0.6 g vanisperce 1.5 g oak powder 2 g blacksmoke 1.5 g
Les électrodes conformes à l'invention ont été obtenues en intro- The electrodes according to the invention were obtained by introducing
duisant dans ces mélanges, environ 50 % en volume, de polypyrol en poudre dopé par des perchlorates et représenté par la formule l(c 4 H 3 N)+ 0, 33y 0,33 (C 104) l 1 présentant une conductivité de l'ordre de 80-L cm a in these blends, about 50% by volume, of perchlorate-doped polypyrol powder and represented by the formula I (c 4 H 3 N) + 0.33 0.33 (C 104) 11 having a conductivity of order of 80-L cm a
Pour les électrodes témoins, on a obtenu un pourcentage d'utili- For the control electrodes, a percentage of use was
sation de la matière active, d'environ 60 %, ce qui pour des électrodes négatives et positives comportant respectivement 3 g de plomb ou de Pb O 2 of the active ingredient, about 60%, which for negative and positive electrodes with 3 g lead or Pb O 2 respectively
se traduit par des capacités respectives de 0,47 Ah et 0,40 Ah. translates into respective capacities of 0.47 Ah and 0.40 Ah.
Pour les électrodes conformes à l'invention, le pourcentage d'uti- For the electrodes according to the invention, the percentage of use
lisation de la matière active était de 85 % et les capacités respectives the active ingredient was 85% and the respective
2 5191912 519191
4 -4 -
des électrodes négatives et positives de 0,33 Ah et 0,28 Ah. Negative and positive electrodes of 0.33 Ah and 0.28 Ah.
Bien entendu l'invention n'est nullement limitée au mode de réali- Naturally, the invention is in no way limited to the embodiment of
sation décrit ci-dessus.described above.
--
Claims (7)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8124214A FR2519191A1 (en) | 1981-12-24 | 1981-12-24 | ACTIVE MATERIAL FOR LEAD-ACRYLIC ELECTRODES |
EP82111851A EP0083059A1 (en) | 1981-12-24 | 1982-12-21 | Active material for lead accumulator electrodes |
JP57234950A JPS58115764A (en) | 1981-12-24 | 1982-12-23 | Electrode active substance for lead storage battery |
CA000418421A CA1176702A (en) | 1981-12-24 | 1982-12-23 | Active matter for lead-acid batteries |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8124214A FR2519191A1 (en) | 1981-12-24 | 1981-12-24 | ACTIVE MATERIAL FOR LEAD-ACRYLIC ELECTRODES |
Publications (2)
Publication Number | Publication Date |
---|---|
FR2519191A1 true FR2519191A1 (en) | 1983-07-01 |
FR2519191B1 FR2519191B1 (en) | 1984-04-06 |
Family
ID=9265394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR8124214A Granted FR2519191A1 (en) | 1981-12-24 | 1981-12-24 | ACTIVE MATERIAL FOR LEAD-ACRYLIC ELECTRODES |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0083059A1 (en) |
JP (1) | JPS58115764A (en) |
CA (1) | CA1176702A (en) |
FR (1) | FR2519191A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2748982C1 (en) * | 2020-11-16 | 2021-06-02 | Борис Зиновьевич Лубенцов | Electrolyte for improving the electrical characteristics of lead-acid batteries (lab), the application of semidine to improve the electrical characteristics of lab, the method for manufacturing lab electrodes and the method for repairing lab |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3223544A1 (en) * | 1982-06-24 | 1983-12-29 | Basf Ag, 6700 Ludwigshafen | PYRROL COPOLYMERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
FR2553581A1 (en) * | 1983-10-12 | 1985-04-19 | Europ Accumulateurs | Active material for electrodes of lead storage batteries. |
FI74715C (en) * | 1985-07-24 | 1988-03-10 | Neste Oy | ELEVATED POLYTIOFEN OCH FOERFARANDE FOER DESS FRAMSTAELLNING OCH ANVAENDNING. |
GB8600894D0 (en) * | 1986-01-15 | 1986-02-19 | Atomic Energy Authority Uk | Electrochemical cells |
US5027161A (en) * | 1987-09-17 | 1991-06-25 | Canon Kabushiki Kaisha | Image forming apparatus |
DE102013225570A1 (en) * | 2013-12-11 | 2015-06-11 | Robert Bosch Gmbh | Binder materials for anode and cathode materials of lithium cells |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2514415A (en) * | 1946-02-27 | 1950-07-11 | Carl H Rasch | Storage battery paste with ion exchange expander |
FR1063719A (en) * | 1951-09-27 | 1954-05-05 | Bosch Gmbh Robert | Electric system with variable ionic concentration, in particular accumulator battery |
FR94536E (en) * | 1967-02-20 | 1969-08-29 | Centre Nat Rech Scient | Electrodes based on organic semiconductors and electrochemical generators using such electrodes. |
US4222903A (en) * | 1978-05-04 | 1980-09-16 | University Patents, Inc. | P-Type electrically conducting doped polyacetylene film and method of preparing same |
EP0036118A2 (en) * | 1980-03-11 | 1981-09-23 | University Patents, Inc. | Secondary batteries based on reversible electrochemical doping of conjugated polymers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5652868A (en) * | 1979-10-05 | 1981-05-12 | Citizen Watch Co Ltd | Solid-electrolyte battery |
-
1981
- 1981-12-24 FR FR8124214A patent/FR2519191A1/en active Granted
-
1982
- 1982-12-21 EP EP82111851A patent/EP0083059A1/en not_active Ceased
- 1982-12-23 JP JP57234950A patent/JPS58115764A/en active Pending
- 1982-12-23 CA CA000418421A patent/CA1176702A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2514415A (en) * | 1946-02-27 | 1950-07-11 | Carl H Rasch | Storage battery paste with ion exchange expander |
FR1063719A (en) * | 1951-09-27 | 1954-05-05 | Bosch Gmbh Robert | Electric system with variable ionic concentration, in particular accumulator battery |
FR94536E (en) * | 1967-02-20 | 1969-08-29 | Centre Nat Rech Scient | Electrodes based on organic semiconductors and electrochemical generators using such electrodes. |
US4222903A (en) * | 1978-05-04 | 1980-09-16 | University Patents, Inc. | P-Type electrically conducting doped polyacetylene film and method of preparing same |
EP0036118A2 (en) * | 1980-03-11 | 1981-09-23 | University Patents, Inc. | Secondary batteries based on reversible electrochemical doping of conjugated polymers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2748982C1 (en) * | 2020-11-16 | 2021-06-02 | Борис Зиновьевич Лубенцов | Electrolyte for improving the electrical characteristics of lead-acid batteries (lab), the application of semidine to improve the electrical characteristics of lab, the method for manufacturing lab electrodes and the method for repairing lab |
Also Published As
Publication number | Publication date |
---|---|
EP0083059A1 (en) | 1983-07-06 |
FR2519191B1 (en) | 1984-04-06 |
CA1176702A (en) | 1984-10-23 |
JPS58115764A (en) | 1983-07-09 |
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